Despite being multifaceted in nature, positive emotional (PE) experiences often are studied using only global PE ratings, and measures assessing more specific PE facets do not converge in their assessment approaches. To address these issues, we examined hierarchical factor structures of ratings of positive emotionality, which reflect propensities toward experiencing PE, in both online community adult (N = 375) and undergraduate (N = 447) samples. Preregistered analyses indicated (a) a broad distinction between tendencies to experience social affection and other PE types, and that (b) PE ratings can be differentiated by as many as four replicable factors of Joviality, Social Affection, Serenity, and Attentiveness. These PE dimensions were associated with distinct personality and psychopathology profiles. Examples of these distinctive associations included Joviality displaying robust positive associations with grandiosity and exhibitionism; conversely, although Social Affection and Joviality were strongly correlated, Social Affection showed associations in the opposite direction with grandiosity and exhibitionism. Other notable results include Serenity (e.g., feeling relaxed) showing negative associations with negative emotionality at a magnitude indicating that Serenity may reflect low levels of negative emotionality to a considerable degree. Collectively, these results highlight the need to consider distinct PE facets in addition to global PE ratings when assessing PE, as important nuance may be lost otherwise. Furthermore, our results indicate the need for additional research clarifying PE structure at different levels of abstraction to inform future measure development efforts and assessment approaches. (PsycInfo Database Record (c) 2021 APA, all rights reserved).